A concentration-gradient composition is proposed as an effective approach
to solve the mechanical degradation and improve the electrochemical cyclability for cathodes of sodium-ion batteries. Concentration-gradient shell NaxNiyMn1-yFe(CN)6·nH2O, in which the Ni content gradually increases from the interior to the particle surface, is synthesized by a facile co-precipitation process. The as-obtained cathode exhibits an improved electrochemical performance compared to homogeneous NaxMnFe(CN)6·nH2O, delivering a high reversible specific capacity of 110 mA h g-1 at 0.2 C and outstanding cycling stability (93% retention after 1000 cycles at 5 C). The improvement of electrochemical performance can be attributed to its robust microstructure that effectively
alleviates the electrochemically induced stresses and accumulated damage during sodiation/desodiation and thus prevents the initiation of fracture in the particles upon long term cycling. These findings render a prospective strategy to develop high-performance electrode materials for sodium-ion batteries.
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Measurement of Volume Changes and Associated Stresses in Ge Electrodes Due to Na/Na + Redox Reactions
In situ electrochemical cells were assembled with an amorphous germanium (a-Ge) film as working electrode and sodium foil as reference and counter electrode. The stresses generated in a-Ge electrodes due to electrochemical reaction with sodium were measured in real-time during the galvanostatic cycling. A specially designed patterned a-Ge electrode was cycled against sodium and the corresponding volume changes were measured using an AFM; it was observed that sodiation/desodiation of a-Ge results in more than 300% volume change, consistent with literature. The potential and stress response showed that the a-Ge film undergoes irreversible changes during the first sodiation process, but the subsequent desodiation/sodiation cycles are reversible. The stress response of the film reached steady-state after the initial sodiation and is qualitatively similar to the response of Ge during lithiation, i.e., initial linear elastic response followed by extensive plastic deformation of the film to accommodate large volume changes. However, despite being bigger ion, sodiation of Ge generated lower stress levels compared to lithiation. Consequently, the mechanical dissipation losses associated with plastic deformation are lower during sodiation process than it is for lithiation.
more » « less- NSF-PAR ID:
- 10209110
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 168
- Issue:
- 1
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- Article No. 010504
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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A concentration-gradient composition is proposed as an effective approach to solve the mechanical degradation and improve the electrochemical cyclability for cathodes of sodium-ion batteries. Concentration-gradient shell NaxNiyMn1-yFe(CN)6·nH2O, in which the Ni content gradually increases from the interior to the particle surface, is synthesized by a facile co-precipitation process. The as-obtained cathode exhibits an improved electrochemical performance compared to homogeneous NaxMnFe(CN)6·nH2O, delivering a high reversible specific capacity of 110 mA h g-1 at 0.2 C and outstanding cycling stability (93% retention after 1000 cycles at 5 C). The improvement of electrochemical performance can be attributed to its robust microstructure that effectively alleviates the electrochemically induced stresses and accumulated damage during sodiation/desodiation and thus prevents the initiation of fracture in the particles upon long term cycling. These findings render a prospective strategy to develop high-performance electrode materials for sodium-ion batteries.more » « less
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